JP4326703B2 - Solvent-free white fine powder of copolymer of maleic anhydride and C1-C4 alkyl vinyl ether substantially free of poly (alkyl vinyl ether) homopolymer - Google Patents
Solvent-free white fine powder of copolymer of maleic anhydride and C1-C4 alkyl vinyl ether substantially free of poly (alkyl vinyl ether) homopolymer Download PDFInfo
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- JP4326703B2 JP4326703B2 JP2000605646A JP2000605646A JP4326703B2 JP 4326703 B2 JP4326703 B2 JP 4326703B2 JP 2000605646 A JP2000605646 A JP 2000605646A JP 2000605646 A JP2000605646 A JP 2000605646A JP 4326703 B2 JP4326703 B2 JP 4326703B2
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- vinyl ether
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- -1 C1-C4 alkyl vinyl ether Chemical compound 0.000 title claims description 30
- 229920001577 copolymer Polymers 0.000 title claims description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims description 18
- 229920001519 homopolymer Polymers 0.000 title claims description 16
- 239000000843 powder Substances 0.000 title claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 241001550224 Apha Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Emergency Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【０００１】
（発明の技術分野）
本発明は、無水マレイン酸及びC1-C4アルキルビニルエーテルの共重合体に関するものであり、特には、ポリ(アルキルビニルエーテル)単独重合体を実質的に含まない共重合体に関するものである。
【０００２】
（従来の技術）
無水マレイン酸(MAN)及びC1-C4アルキルビニルエーテル(AVE)の共重合体は、当該技術分野において広範囲に記載されてきた。しかし、このような共重合体生成物は、反応混合物中に存在する過剰量のアルキルビニルエーテルが単独重合する結果、不純物としてポリ(アルキルビニルエーテル)単独重合体を常に含んでいる。このポリ(アルキルビニルエーテル)不純物が存在すると、パーソナルケア及びオーラルケアの組成物として共重合体生成物から作られるあらゆる共重合体加水分解生成物の性能に悪影響を与える。特に、この不純物は、このような組成物に好ましくない色及び濁りを与える。
【０００３】
それゆえ、本発明の目的は、無水マレイン酸及びC1-C4アルキルビニルエーテルからなる共重合体の無溶剤白色微粉末であって、ポリ(アルキルビニルエーテル)単独重合体をNMR分析の検出限界程度、つまり1mol%未満の範囲でしか含まない当該無溶剤白色微粉末を提供することである。
【０００４】
本発明のもう一つの目的は、このような高純度の共重合体を作るための溶剤を使用しない製造方法を提供することである。
【０００５】
本発明の特徴は、無水マレイン酸と、過剰量のアルキルビニルエーテルと、ラジカル重合開始剤とからなる反応混合物中に抑制剤を含有させることである。抑制剤は、これらのモノマーがラジカル共重合する間にアルキルビニルエーテルモノマーがカチオン単独重合するのを防止するのに充分な量だけ反応混合物中に存在させる。
【０００６】
本発明のもう一つの特徴は、アルキルビニルエーテル単独重合体を含まない無水マレイン酸及びアルキルビニルエーテルの共重合体の加水分解物であって、色や濁りのない当該加水分解物を提供することである。
【０００７】
（課題を解決する方法）
実質的にポリ(アルキルビニルエーテル)を含まない、無水マレイン酸及びC1-C4アルキルビニルエーテルからなる共重合体の無溶剤白色微粉末についてここに記載する。
【０００８】
本発明の特徴は、NMR分析の検出限界範囲までしか前記単独重合体を含まない前記共重合体を提供することである。
【０００９】
抑制剤は、プロセス中で使用するアルキルビニルエーテルモノマーの重量に対して約500重量ppmから約5000重量ppm存在させるのが好ましい。
【００１０】
アルキルビニルエーテルのカチオン単独重合を阻止するために好ましい抑制剤としては、水、アルコール、アンモニア、アミン、ヒドロキシアミン、アミド又はカルボン酸、トリアルキルホスフィン又はトリアリールホスフィン、チオフェン、及びエステルを含む。好ましくは水である。
【００１１】
（発明の実施の形態）
本発明は、無水マレイン酸と、メチルビニルエーテル(MVE)とするのが好ましいC1-C4アルキルビニルエーテルとからなる共重合体の無溶剤白色微粉末であって、アルキルビニルエーテルモノマーの単独重合体、即ちポリ(アルキルビニルエーテル)単独重合体を実質的に含まない当該無溶剤白色微粉末を製造するための溶剤を使用しない製造方法を提供するものである。これらの単独重合体は、反応混合物中に存在する過剰量のアルキルビニルエーテルが単独重合することにより通常は生成される。
【００１２】
本発明においては、反応混合物中にアルキルビニルエーテルの単独重合抑制剤を含ませることにより、アルキルビニルエーテルモノマーがカチオン単独重合することを防止する一方で、無水マレイン酸及びアルキルビニルエーテルモノマーの所望のフリーラジカル共重合は容易に起こりうるようにする。
【００１３】
本発明で使用するのに好ましい抑制剤としては、水、アルコール、アンモニア、アミン、ヒドロキシアミン、アミド、ホスフィン、チオフェン、カルボン酸、及びエステルを含む。水が最も好ましい。
【００１４】
抑制剤として、水を、アルキルビニルエーテルの重量の約500重量ppmから約5000重量ppm程度の十分な量で存在させるのが好ましい。もちろん、望むのであれば、これを超過した量でも使用できる。
【００１５】
好ましくは、MAN:MVEのモル比率を少なくとも3:1とし、より好ましくは25:1から5:1とし、最も好ましくは12:1から7:1とする。重合中の固体レベルパーセントは10%から40%である。
【００１６】
フリーラジカル重合開始剤の濃度は、得られる共重合体に対して約0.01重量%から約0.2重量%、好ましくは約0.05重量%から約0.1重量%である。
【００１７】
通常、共重合生成物中で検出される単独重合体の濃度は様々である。共重合させる際に抑制剤を使用すると、この単独重合体の量が、共重合物をNMR分析する際の検出限界より低いレベル、即ち単独重合体が１%未満にまで減少する。
【００１８】
共重合の完了後、過剰なMVEを取り除き、共重合体を減圧下で約40℃から約100℃で乾燥する。
【００１９】
本発明を以下の実施例を参照にして説明する。
【００２０】
実施例１
Ｂｕｃｈｉ社製の１リットル圧力リアクターに窒素を分散させ、メチルビニルエーテルMVE300g(5.16mol)と、Trigonox(登録商標)21(t-ブチルパーオキシ-2-エチルヘキサノート、Akzo Nobel chemicals 社)0.55g(得られる共重合物を基準に0.08%)とを充填しMVEでリンスした。次に3000ppm(MVE基準)の水を加えた。このように充填したリアクターを15分にわたって撹拌しながら75℃に熱した。それから41g(0.418mol)の溶融無水マレイン酸MAN(MVE:MANが15:1)を１時間にわたって加えた。得られた反応混合物の固体含有量は16%だった。温度を75℃として1.5時間保持した。そして、過剰なMVEを取り除いて、気圧を大気圧に下げた。リアクターを開けると、自由に流動する共重合体の微小粉末生成物が観察された。得られた生成物は真空乾燥機内で65℃で４時間乾燥し、残留している微量のMVEを全て取り除いた。
【００２１】
合計で64.8gの自由に流動する微小粉末を回収した(理論収率の99.37%)。生成物はMAN:MVEが1:1の共重合体で(13C NMRによる)、比粘度は3.6であった(25℃のメチルビニルケトン中１% w/v)。NMR分析では１%未満のポリ(メチルビニルエーテル)単独重合体しか検出されなかった。
【００２２】
共重合体の13%水溶液の濁り度及びＡＰＨＡカラーは、25NTU/60にしか相当せず、実質的に濁り及び色の無い共重合体の加水分解生成物が得られていたことが示された。オーラルケア組成物中の風味特性は完全に許容できるものであった。
【００２３】
実施例２
5000ppmの水を予め充填しておいた反応混合物中に加えて実施例１の方法に従って実験を行った。ポリ(メチルビニルエーテル)単独重合体はNMR分析では検出されなかった。共重合体の比粘度は3.0であった。13%水溶液の濁り度及びＡＰＨＡカラーはそれぞれ20/45で、かつオーラルケア組成物中の風味特性は完全に許容できるものであった。
【００２４】
本発明を特定の実施例を参照して説明したが、当業者は、本発明に変更及び変型を加えうることを理解するであろう。すなわち、本発明は特許請求の範囲の記載によってのみ限定されることを意図するものである。[0001]
(Technical field of the invention)
The present invention relates to a copolymer of maleic anhydride and a C 1 -C 4 alkyl vinyl ether, and more particularly to a copolymer substantially free of a poly (alkyl vinyl ether) homopolymer.
[0002]
(Conventional technology)
Copolymers of maleic anhydride (MAN) and C 1 -C 4 alkyl vinyl ethers (AVE) have been extensively described in the art. However, such copolymer products always contain poly (alkyl vinyl ether) homopolymer as an impurity as a result of homopolymerization of excess alkyl vinyl ether present in the reaction mixture. The presence of this poly (alkyl vinyl ether) impurity adversely affects the performance of any copolymer hydrolysis product made from the copolymer product as a personal care and oral care composition. In particular, this impurity gives undesirable color and turbidity to such compositions.
[0003]
Therefore, an object of the present invention is a solvent-free white fine powder of a copolymer comprising maleic anhydride and a C 1 -C 4 alkyl vinyl ether, and the poly (alkyl vinyl ether) homopolymer has a detection limit of about NMR analysis. That is, to provide the solvent-free white fine powder which is contained only in the range of less than 1 mol%.
[0004]
Another object of the present invention is to provide a production method that does not use a solvent for producing such a high purity copolymer.
[0005]
A feature of the present invention is that an inhibitor is contained in a reaction mixture composed of maleic anhydride, an excess amount of an alkyl vinyl ether, and a radical polymerization initiator. The inhibitor is present in the reaction mixture in an amount sufficient to prevent the alkyl vinyl ether monomer from cationic homopolymerization during the radical copolymerization of these monomers.
[0006]
Another feature of the present invention is to provide a hydrolyzate of a copolymer of maleic anhydride and alkyl vinyl ether that does not contain an alkyl vinyl ether homopolymer, and has no color or turbidity. .
[0007]
(How to solve the problem)
Described herein is a solvent-free white fine powder of a copolymer of maleic anhydride and C 1 -C 4 alkyl vinyl ether that is substantially free of poly (alkyl vinyl ether).
[0008]
A feature of the present invention is to provide the copolymer containing the homopolymer only up to the detection limit range of NMR analysis.
[0009]
The inhibitor is preferably present from about 500 ppm to about 5000 ppm by weight based on the weight of the alkyl vinyl ether monomer used in the process.
[0010]
Preferred inhibitors for preventing cationic homopolymerization of alkyl vinyl ethers include water, alcohols, ammonia, amines, hydroxyamines, amides or carboxylic acids, trialkylphosphines or triarylphosphines, thiophenes, and esters. Preferably it is water.
[0011]
(Embodiment of the Invention)
The present invention is a solvent-free white fine powder of a copolymer comprising maleic anhydride and a C 1 -C 4 alkyl vinyl ether, preferably methyl vinyl ether (MVE), which is a homopolymer of an alkyl vinyl ether monomer, That is, the present invention provides a production method that does not use a solvent for producing the solvent-free white fine powder substantially free of a poly (alkyl vinyl ether) homopolymer. These homopolymers are usually produced by homopolymerization of excess alkyl vinyl ether present in the reaction mixture.
[0012]
In the present invention, the alkyl vinyl ether homopolymerization inhibitor is included in the reaction mixture to prevent the alkyl vinyl ether monomer from cationic homopolymerization, while the desired free radical copolymerization of maleic anhydride and alkyl vinyl ether monomer. Polymerization should be easy to occur.
[0013]
Preferred inhibitors for use in the present invention include water, alcohols, ammonia, amines, hydroxyamines, amides, phosphines, thiophenes, carboxylic acids, and esters. Water is most preferred.
[0014]
As an inhibitor, water is preferably present in a sufficient amount of about 500 ppm to about 5000 ppm by weight of the alkyl vinyl ether. Of course, you can use more than this if you want.
[0015]
Preferably, the molar ratio of MAN: MVE is at least 3: 1, more preferably from 25: 1 to 5: 1, most preferably from 12: 1 to 7: 1. The percent solids level during polymerization is 10% to 40%.
[0016]
The concentration of the free radical polymerization initiator is about 0.01% to about 0.2% by weight, preferably about 0.05% to about 0.1% by weight, based on the resulting copolymer.
[0017]
Usually, the concentration of homopolymer detected in the copolymerized product varies. When an inhibitor is used in the copolymerization, the amount of the homopolymer is reduced to a level lower than the detection limit when the copolymer is subjected to NMR analysis, that is, the homopolymer is reduced to less than 1%.
[0018]
After completion of the copolymerization, excess MVE is removed and the copolymer is dried at about 40 ° C. to about 100 ° C. under reduced pressure.
[0019]
The invention will now be described with reference to the following examples.
[0020]
Example 1
Nitrogen was dispersed in a Buchi 1 liter pressure reactor, and 300 g (5.16 mol) of methyl vinyl ether MVE and 0.55 g of Trigonox (registered trademark) 21 (t-butylperoxy-2-ethylhexanote, Akzo Nobel chemicals) 0.08%) based on the copolymer obtained, and then rinsed with MVE. Next, 3000 ppm (MVE standard) water was added. The so-filled reactor was heated to 75 ° C. with stirring for 15 minutes. Then 41 g (0.418 mol) of molten maleic anhydride MAN (MVE: MAN 15: 1) was added over 1 hour. The solid content of the resulting reaction mixture was 16%. The temperature was maintained at 75 ° C. for 1.5 hours. Then, excess MVE was removed and the pressure was reduced to atmospheric pressure. Upon opening the reactor, a free flowing copolymer micropowder product was observed. The obtained product was dried at 65 ° C. for 4 hours in a vacuum dryer to remove all remaining traces of MVE.
[0021]
A total of 64.8 g of free flowing fine powder was recovered (99.37% of theoretical yield). The product was a 1: 1 MAN: MVE copolymer (by 13 C NMR) with a specific viscosity of 3.6 (1% w / v in methyl vinyl ketone at 25 ° C.). NMR analysis detected less than 1% poly (methyl vinyl ether) homopolymer.
[0022]
The turbidity and APHA color of a 13% aqueous solution of the copolymer corresponded only to 25 NTU / 60, indicating that a substantially hydrolyzed and colorless copolymer hydrolysis product was obtained. . The flavor characteristics in the oral care composition were completely acceptable.
[0023]
Example 2
The experiment was performed according to the method of Example 1 with 5000 ppm water added to the pre-filled reaction mixture. Poly (methyl vinyl ether) homopolymer was not detected by NMR analysis. The specific viscosity of the copolymer was 3.0. The turbidity and APHA color of the 13% aqueous solution were 20/45, respectively, and the flavor characteristics in the oral care composition were completely acceptable.
[0024]
Although the present invention has been described with reference to particular embodiments, those skilled in the art will appreciate that modifications and variations can be made to the present invention. In other words, the present invention is intended to be limited only by the description of the scope of claims.
Claims (2)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/270,176 | 1999-03-16 | ||
| US09/270,176 US6211318B1 (en) | 1997-10-02 | 1999-03-16 | Solvent-free, fine white powders of a copolymer of maleic anhydride and A C1-C4 alkyl vinyl ether substantially free of poly (alkyl vinyl ether, homopolymer |
| PCT/US2000/005688 WO2000055220A1 (en) | 1999-03-16 | 2000-03-02 | Solvent-free, fine white powders of a copolymer of maleic anhydride and a c1-c4 alkyl vinyl ether substantially free of poly(alkyl vinyl ether) homopolymer |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2002539301A JP2002539301A (en) | 2002-11-19 |
| JP2002539301A5 JP2002539301A5 (en) | 2007-04-19 |
| JP4326703B2 true JP4326703B2 (en) | 2009-09-09 |
Family
ID=23030227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000605646A Expired - Fee Related JP4326703B2 (en) | 1999-03-16 | 2000-03-02 | Solvent-free white fine powder of copolymer of maleic anhydride and C1-C4 alkyl vinyl ether substantially free of poly (alkyl vinyl ether) homopolymer |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6211318B1 (en) |
| EP (1) | EP1198486B1 (en) |
| JP (1) | JP4326703B2 (en) |
| AT (1) | ATE305946T1 (en) |
| AU (1) | AU3723600A (en) |
| DE (1) | DE60023009T2 (en) |
| WO (1) | WO2000055220A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6692725B2 (en) * | 2001-02-19 | 2004-02-17 | Daicel Chemical Industries, Ltd. | Composition for oral care |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE380814A (en) * | 1930-06-26 | |||
| US2782181A (en) * | 1954-02-23 | 1957-02-19 | Goodyear Tire & Rubber | Oxidizable rubber containing a phthalidyl phenol as antioxidant |
| US3003988A (en) * | 1958-10-16 | 1961-10-10 | Clark Cleveland Inc | Stabilizer for dentures |
| US3868432A (en) * | 1972-04-13 | 1975-02-25 | Warner Lambert Co | Denture adhesive preparation |
| JPS57172949A (en) * | 1981-04-17 | 1982-10-25 | Kanegafuchi Chem Ind Co Ltd | One-pack composition |
| JPS61127709A (en) * | 1984-11-27 | 1986-06-16 | Sumitomo Chem Co Ltd | Production of ethylene copolymer |
| US4627977A (en) * | 1985-09-13 | 1986-12-09 | Colgate-Palmolive Company | Anticalculus oral composition |
| US5166271A (en) * | 1988-09-12 | 1992-11-24 | Mitsui Toatsu Chemicals, Inc. | Heat resistant polyvinyl chloride copolymer and preparation process of the copolymer |
| US4962185A (en) * | 1989-10-02 | 1990-10-09 | Gaf Chemicals Corporation | Process of rendering copolymer powders of maleic anhydride and an alkyl vinyl ether prepared in benzene solvent substantially benzene-free |
| US5147963A (en) * | 1989-10-16 | 1992-09-15 | Isp Investments Inc. | Process for the production of amorphous methyl vinyl ether homopolymers having a high molecular weight and narrow molecular weight distribution |
| US5449715A (en) * | 1991-09-17 | 1995-09-12 | Isp Investments Inc. | Colorless, non-toxic, stabilized aqueous solution of a C1-C5 alkyl vinyl ether and maleic acid copolymers |
| US5214089A (en) * | 1991-09-18 | 1993-05-25 | Isp Investments Inc. | Stabilized aqueous solution of a C1 -C5 alkyl vinyl ether and maleic acid copolymer |
| US5369145A (en) * | 1993-06-14 | 1994-11-29 | Block Drug Company | Denture adhesive |
| US5939506A (en) * | 1997-10-02 | 1999-08-17 | Isp Investments Inc. | Solvent-free process for making high molecular weight terpolymers of maleic anhydride, C1 -C4 alkyl vinyl ether and isobutylene |
-
1999
- 1999-03-16 US US09/270,176 patent/US6211318B1/en not_active Expired - Lifetime
-
2000
- 2000-03-02 AT AT00916073T patent/ATE305946T1/en not_active IP Right Cessation
- 2000-03-02 WO PCT/US2000/005688 patent/WO2000055220A1/en not_active Ceased
- 2000-03-02 DE DE60023009T patent/DE60023009T2/en not_active Expired - Lifetime
- 2000-03-02 AU AU37236/00A patent/AU3723600A/en not_active Abandoned
- 2000-03-02 EP EP00916073A patent/EP1198486B1/en not_active Expired - Lifetime
- 2000-03-02 JP JP2000605646A patent/JP4326703B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1198486A4 (en) | 2004-10-27 |
| WO2000055220A1 (en) | 2000-09-21 |
| DE60023009D1 (en) | 2006-02-16 |
| ATE305946T1 (en) | 2005-10-15 |
| JP2002539301A (en) | 2002-11-19 |
| DE60023009T2 (en) | 2006-06-22 |
| EP1198486A1 (en) | 2002-04-24 |
| EP1198486B1 (en) | 2005-10-05 |
| US6211318B1 (en) | 2001-04-03 |
| AU3723600A (en) | 2000-10-04 |
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